Sulfate-bearing soils are a problem in highway construction as they combine with materials used for lime stabilization to form minerals, particularly ettringite, that expand and induce heave in the stabilized soil. This research involves quantifying sulfate in soils that may be potentially used in highway construction using electromagnetic induction. The objectives are to: 1) document electrical conductivity (EC) variability within selected sites that contain sulfate-bearing materials, and 2) determine if electromagnetic induction has potential for locating hazardous levels of sulfate-bearing materials. The 0.43 ha study area is located in the Blackland Prairies and is a Vertisol known to contain gypsum at the time of site selection. Apparent EC using a model EM38 electromagnetic induction instrument was measured at 200 locations in July and November 2003, using a sampling grid with 5-m spacings. Representative rows and columns were selected from the map of apparent electrical conductivity, and soil cores taken to a depth of 1.5 m at 29 points. Soil samples were obtained by dividing cores into depth increments of 0 to 25 cm, 25 to 75 cm, and 75 to 150 cm. Laboratory analyses were run for each sample and included moisture content, EC and soluble cations and anions of the saturated paste extract, and percent gypsum. Elevation measurements were made to determine if changes in elevation related to EC measurements. Apparent EC proved to be more successful at detecting soluble salts during the dry sampling period (July) when the effect of soil moisture content was less. For July data, EC and gypsum were significantly correlated in the deepest samples (r2 = 0.51 and 0.15, respectively) to apparent EC. Further, soluble sulfate was significantly correlated to apparent EC (r2 = 0.30) at a depth of 25 to 75 cm. Results suggest that the EM38 can be used successfully to map variability of soil salinity across a field, but although correlation exists between apparent EC and sulfate-bearing materials, it is not sufficiently strong to serve as a good predictor for conditions surrounding lime-induced heave in soil.

Since 2006, research funded by the Texas Department of Transportation (TxDOT) has evaluated the use of coatings and sealers for mitigating expansion due to alkali-silica reaction (ASR) and/or delayed ettringite formation (DEF) in hardened concrete. The report herein includes a project summary of previous work in Phase I, led by Racheal Lute (2008) and Charles Rust (2009). The Phase II research, described in this thesis, established concrete exposure blocks and NCHRP 244 Series II testing as the cornerstones of characterizing coating effectiveness. The studies assessed coating system performance by examining the contribution of steel reinforcement, the effects of aggregate reactivity, the size limitations of treatments, and the impact of painted concrete substrates. Lastly, this thesis describes the preliminary results of a field study site of columns supporting a flyover, and a concrete exposure block site in Houston, Texas. Overall, the results are encouraging as several coatings have reduced expansion by lowering internal relative humidity.

The effect of the sulfates and alkalis on the durability of Portland cement systems was investigated through a series of cube and prism mixes. Durability was assessed using expansion of mortar prisms and the compressive strength of mortar cubes. The study covered a large range of both alkali and sulfate contents using 5 different Portland cements. The alkali contents ranged from 0.27 to 3.8%, the sulfate content (as SO3) ranged from 2.54 to 5%. Doping was done using Terra Alba gypsum and potassium hydroxide. In addition to physical measurements, SEM, XRD, chemical analysis and heat of hydration calorimetry were used for further analysis. Mixing, curing and testing were done at room temperature. The results show that sulfate contents up to the levels used in this study, at low alkali contents and ambient temperature curing, did not adversely affect durability of Portland cement mortars up to 360 days. A correlation was established between expansion and ettringite formation. Increasing the alkali content always resulted in loss of compressive strength, and in some cases, excessive expansion. Excessive expansion was only experienced at the 3.8% level. Alkali levels of up to 2% and sulfate levels of 5% did not result in excessive expansion at room temperature-cure up to the ages reported here. The effect of alkali depended on thecement mineralogical composition, especially C3S content. The addition of alkalis seems to impact the nature of the microstructure and the nature of other hydration products. The addition of sulfates seems to counteract the effect of alkalis, especially on the loss of compressive strength. However, these sulfates may result in other problems as they may be available at any time to form ettringite which may, under certain conditions, result in excessive expansion. It was concluded that sulfate levels on the order of 3-3.6%, did not pose any major durability drawbacks under normal curing temperatures and low alkali contents (<1%). Alkali levels above 1% will adversely affect the durability of Portland cement systems.

Alkali-silica reaction (ASR) and delayed ettringite formation (DEF) deterioration have been a problem for the concrete infrastructure in the state of Texas and around the world in recent decades. A great deal of research into the causes and mechanisms of the deterioration has helped to prevent the formation of ASR and DEF in new construction, but the evaluation and maintenance of existing structures remains a problem. The goal of this research is to investigate the use of several nondestructive testing (NDT) methods to evaluate the level of ASR and DEF deterioration in a structural element. Based on the results, recommendations are made as to which NDT methods have the most potential to be incorporated into the evaluation process. / text

The prediction of the expected long-term performance of concrete exposed to sewage and similar materials can be difficult as it is affected by a large number of parameters. In addition, the deterioration process in concrete is generally slow. The focus of the study was to ascertain the life expectancy of concrete septic tanks located in rural Victoria. In developing the accelerated test method, ASTM C 192, ASTM C 452, ASTM C 1293 and ASTM C 109 standard procedures were adopted wherever possible. From the analysis of mass change data after 350 days, it was found that the mass change rate for concrete in sulphate solutions increases with the increase of concentration of Na2SO4 solution. The weights of the samples in Na2SO4 solution increased with time, whereas the control specimens lost weight as a result of heating cycles. The probable reason for weight increase in Na2SO4 solution was hypothesized as the formation of gypsum (CaSO4.2H2O) and ettringite (3CaO.Al2O.3CaSO4.32H2O), which is confirmed from microstructural analysis. The rate of weight gain was higher at the beginning and reduced with time. The stronger the concentration of Na2SO4 the stronger was the weight gain or expansion of mass. All the samples in sulphate solutions attained their maximum weight at around 250 days. For the specimens in sulphuric acid solutions weight loss was observed to be higher for higher concentrations. The lower the pH of the acidic solutions, the larger was the weight loss. The weight loss of specimens in acidic solutions exceeded the control specimen after 250 days. The reason for the loss of weight of the samples in sulphuric acid may be the decalcification of C-S-H gel within the concrete, and as a consequence the loss of cementitious structure. Comparison of the corrosion of concrete and also microstructural examination of field samples confirmed that the deterioration mechanism is similar to that observed in the laboratory. The accelerated testing adopted here offers a realistic method of predicting the deterioration of septic tanks under biogenic sulphuric acid corrosion. Two equations have been proposed to predict deterioration due to sulphate attack and sulphuric acid attack as mass loss (or gain) with time.

abstract: Expansive soils impose challenges on the design, maintenance and long-term stability of many engineered infrastructure. These soils are composed of different clay minerals that are susceptible to changes in moisture content. Expansive clay soils wreak havoc due to their volume change property and, in many cases, exhibit extreme swelling and shrinking potentials. Understanding what type of minerals and clays react in the presence of water would allow for a more robust design and a better way to mitigate undesirable soil volume change. The relatively quick and widely used method of X-ray Diffraction (XRD) allows identifying the type of minerals present in the soil. As part of this study, three different clays from Colorado, San Antonio Texas, and Anthem Arizona were examined using XRD techniques. Oedometer-type testing was simultaneously preformed in the laboratory to benchmark the behavior of these soils. This analysis allowed performing comparative studies to determining if the XRD technique and interpretation methods currently available could serve as quantitative tools for estimating swell potential through mineral identification. The soils were analyzed using two different software protocols after being subjected to different treatment techniques. Important observations include the formation of Ettringite and Thaumasite, the effect of mixed-layer clays in the interpretation of the data, and the soils being subject to Gypsification. The swelling data obtained from the oedometer-type laboratory testing was compared with predictive swelling functions available from literature. A correlation analysis was attempted in order to find what index properties and mineralogy parameters were most significant to the swelling behavior of the soils. The analysis demonstrated that Gypsification is as important to the swelling potential of the soil as the presence of expansive clays; and it should be considered in the design and construction of structures in expansive soils. Also, the formation of Ettringite and Thaumasite observed during the treatment process validates the evidence of Delayed Ettringite Formation (DEF) reported in the literature. When comparing the measured results with a proposed method from the University of Texas at Arlington (UTA), it was found that the results were somewhat indicative of swell potential but did not explain all causes for expansivity. Finally, it was found that single index properties are not sufficient to estimate the free swell or the swell pressure of expansive soils. In order to have a significant correlation, two or more index properties should be combined when estimating the swell potential. When properties related to the soil mineralogy were correlated with swell potential parameters, the amount of Gypsum present in the soil seems to be as significant to the swell behavior of the soil as the amount of Smectite found. / Dissertation/Thesis / M.S. Civil Engineering 2014

Philosophiae Doctor - PhD / Mine water poses a serious environmental challenge and contains elements such as Fe, Al, and Mn in potentially toxic concentrations. The major anion in mine water is sulphate. The complexity and diversity of mine water composition makes its treatment very expensive, and there is no “one-fits-all” treatment option available for mine water. Active treatment of mine water produces water with good quality but the processes are not sustainable because of the costs. Previous studies have shown that acid mine drainage can be treated with coal FA to produce better quality water. The use of coal FA, a waste material from coal fired power station and mine water would go a long way in achievement of sustainable treatment of mine water as per previous studies. In this study mine water and coal FA were characterized to determine their physiochemical properties. This study linked the modelling results obtained by using the Geochemist’s workbench (GWB) software to the results obtained during the actual treatment of Matla mine water and Rand Uranium mine water using coal FA and lime. The chemistry involved when Matla mine water and Rand Uranium mine water were treated with flocculants was also investigated. Lastly the chemistry and kinetics involved was investigated when mine water was treated with various ameliorants such as Matla coal FA, lime and/or Al(OH)3 using jet loop mixing or overhead stirring. Mine water from Matla coal mine had a pH of 8 and therefore was classified as neutral mine drainage (NMD). Rand Uranium mine water had a pH of less than 3 and therefore was classified as acid mine drainage (AMD). The concentration of sulphate, Na, Ca, Mg, B, Hg, Se and Cd ions in Matla mine water was 1475, 956, 70, 40, 15, 2.43, 1.12 and 0.005 mg/L respectively. The concentration of sulphate, Fe, Ca, Mn, Mg, Al, B, Cr, Pb, U, Cd, Se and As ions in Rand Uranium mine water was 4126, 896, 376, 282, 155, 27, 5.43, 3.15, 0.51, 0.29, 0.007, 0.06 and 0.006 mg/L respectively . These concentrations were above the target water quality range (TWQR) for potable water set by the Department of Water Affairs (DWA) and World Health Organization (WHO). The gross alpha radioactivity was 6.01 Bq/L and gross beta radioactivity was 6.05 Bq/L in Rand Uranium mine water.

L'objectif de cette thèse est de développer un matériau cimentaire monolithe ayant une forte teneur en ettringite, capable de stocker et de déstocker de la chaleur, respectivement, par déshydratation endothermique et réhydratation exothermique. Une étude numérique et expérimentale du stockage de chaleur dans un réacteur thermochimique (prototype) contenant le matériau développé est aussi réalisée dans le cadre de cette étude. Pour atteindre ces objectifs, l'hydratation de différents liants ettringitiques a été suivie par DRX, ATG et MEB. Une simulation thermodynamique de l'hydratation a aussi été effectuée au moyen du logiciel GEMS (Gibbs Energy Minimization Sofware) afin d'optimiser la formulation du matériau. Le réseau poreux du matériau résultant a ensuite été amélioré par moussage chimique. Nous avons aussi étudié la durabilité et la stabilité du matériau ettringitique synthétisé (carbonatation, stabilité à la température, réversibilité du processus de stockage/déstockage sur plusieurs cycles). Pour prédire le comportement du système de stockage, un modèle bidimensionnel, prenant en compte les spécificités du matériau cimentaire, a été utilisé. Le bilan énergétique et massique dans le matériau poreux génère un système d'équations différentielles non-linéaires et couplées. La résolution numérique du système, effectuée en utilisant MatLab (r), est effectuée par discrétisation spatiale en utilisant la méthode des différences finies, et par intégration temporelle des variables d'état (température et pression de vapeur d'eau). La simulation du modèle, basée sur les propriétés mesurées du matériau en laboratoire, est ensuite utilisée comme outil de conception pour réaliser un premier prototype de réacteur thermochimique au laboratoire. Suite à ces essais, un prototype amélioré est ensuite élaboré et testé. Le résultat des essais de stockage et de déstockage de chaleur avec ces deux prototypes ont servi de validation du modèle numérique d'une part, et de preuve de concept du principe de stockage d'autre part. / The objective of this study is to develop an ettringite-based material with high energy storage density in low temperature conditions, allowing to charge and discharge heat by endothermic dehydration and exothermic rehydration, respectively; then to perform the numerical and experimental study of heat storage in a thermochemical reactor containing the produced material (prototype). To achieve these goals, the hydration of ettringite binders was followed by XRD, TGA and SEM. The thermodynamic simulation of the hydration was also performed using GEMS (Gibbs Energy Minimization Sofware). The porous network of the resulting material was improved by chemical foaming. Furthermore, the carbonation, thermal stability and reversibility tests were performed on the produced material. Physicochemical stability of the material over time was followed by XRD, TGA, SEM and IR. To predict the behavior of the storage system, a bidimensional model, taking account the specificities of the cementitious material, was developed. The heat and mass balance in the thermochemical reactor generates a system of non-linear and coupled differential equations. The numerical resolution was first made by spatial discretization using the finite difference method, then by temporal integration of variables (temperature and water vapor pressure) on MatLab (r). The model simulation, with material properties, was used as concept design to build the thermochemical reactor prototype in the laboratory (cylindrical adsorber). The result of heat storage tests with the prototype was used as proof of concept of the principle on the one hand, and a way to validate the numerical model.

La cristallisation du sel dans les pores peut conduire à l'expansion d'une variété de milieux poreux, y compris le béton, la pierre ou les sols. Par exemple, les attaques sulfatiques de matériaux cimentaires peuvent conduire à des cristallisations du gypse ou de l’ettringite, qui peuvent causer un endommagement et limiter la durabilité des structures en béton. Une meilleure compréhension de la façon dont la cristallisation induit la déformation des matériaux cimentaires est une condition préalable à la conception de moyens efficaces pour atténuer les effets néfastes de la cristallisation du sel. Dans cette thèse, nous cherchons à comprendre comment la cristallisation conduit à l'expansion, pour les matériaux à base de ciment dans le cas spécifique de la présence d'ions sulfatiques, qui est un cas pertinent pour la compréhension des attaques sulfatiques. La principale originalité de l'étude a été de réaliser des expériences avec des matériaux granulaires compactés dans des cellules œdométriques ou isochores. Les échantillons testés ont été fabriqués par broyage de pâtes de C3S, de pâtes de ciment Portland ordinaire, ou des mélanges des phases dont ces pâtes sont constituées (par exemple, monosulfoaluminate AFm), puis de les compacter dans des éprouvettes cylindriques sur une hauteur de 2 cm. Dans les cellules, les échantillons compactés sont très perméables et peuvent être saturés avec des solutions de sulfate de sodium en moins d’1 heure. Dans une cellule œdométrique, l'échantillon est empêché de se dilater radialement, mais est autorisé à se dilater axialement: nous avons mesuré comment des injections de solutions induisent une expansion axiale. Dans une cellule isochore, l'échantillon est empêché de se dilater à la fois radialement et axialement: nous avons mesuré comment des injections de solutions provoquent le développement de contraintes axiales et radiales. Un point notable des cellules isochores que nous avons développées est que toute solution s’évacue le long de l'échantillon et peut être récupérée: ainsi, à partir des mesures des concentrations et des volumes de solutions d'entrée et de sortie, la quantité de sulfates restant dans l'échantillon au cours des expériences pourrait être déterminée. En parallèle des mesures de déformation/contrainte, nous avons effectué des caractérisations minéralogiques et microstructurales des échantillons en utilisant une variété de techniques, notamment : la fluorescence X, l’analyse thermogravimétrique, la diffraction des rayons X, la résonance magnétique nucléaire d'aluminium et la microscopie électronique à balayage avec analyse aux rayons X. Les évolutions des concentrations de sortie et de la minéralogie au cours du processus d'injection ont pu être bien prédites avec le logiciel CHESS de modélisation géochimique. Les résultats expérimentaux de la campagne, en conjonction avec les résultats des caractérisations minéralogiques et microstructurales, ont permis de révéler quels sont les principaux paramètres qui régissent l'expansion. Grâce à ce protocole original que nous avons développé, l'expansion ou le développement de contraintes a commencé immédiatement après l'injection de la solution, s’est stabilisé au bout de quelques jours à quelques semaines, et la cristallisation a eu lieu de façon homogène sur toute la hauteur de l'échantillon. En outre, nous avons montré que la cristallisation du gypse contribue à l'expansion. Dans les tests isochores, nous montrons que les deux cristallisations d'ettringite et de gypse peuvent induire des contraintes, et que l'amplitude de ces contraintes dépend linéairement du volume de ces cristaux formés. Les conclusions tirées de cette étude expérimentale permettent de mieux comprendre les processus physiques par lesquels la cristallisation induit une expansion ou des contraintes dans des solides poreux, et permettent d’orienter la modélisation des attaques sulfatiques dans les matériaux cimentaires / In-pore crystallization can lead to expansion of a variety of porous media, including concrete, stone, or soils. For instance, sulfate attacks of cement-based materials can lead to crystallizations of gypsum or ettringite, which may cause damage and limit the durability of concrete structures. A better understanding of how crystallization induces deformation of cementitious materials is a prerequisite to designing efficient ways of mitigating the detrimental effects of salt crystallization. In this thesis, we aim at understanding how crystallization leads to expansion, for cement-based materials in the specific case of the presence of sulfate ions, which is relevant for sulfate attacks. The main originality of the study was to perform experiments with granular materials compacted into oedometric or isochoric cells. The tested samples were manufactured by grinding C3S pastes, regular Portland cement pastes, or mixtures of phases of which those pastes are made (e.g., monosulfoaluminate AFm), and then compacting them within the cell into 2-cm-high cylindrical specimens. In the cells, the highly permeable compacted samples could be flushed with sodium sulfate solutions in less than 1 hour. In an oedometric cell, the sample is prevented from expanding radially, but is allowed to expand axially: we measured how injections of solutions induced an axial expansion. In an isochoric cell, the sample is prevented from expanding both radially and axially: we measured how injections of solutions induced the development of axial and radial stresses. A salient feature of the isochoric cells we developed is that all solution flushed throughout the sample could be recovered: thus, from the measurements of concentrations and volumes of input and output solutions, the amount of sulfate remaining in the sample over the experiments could be determined. In parallel to the deformation/stress measurements, we also performed the mineralogical and microstructural characterizations of the samples before and after testing by using a variety of techniques, including X-ray fluorescence, thermogravimetric analysis, X-ray diffraction, aluminum nuclear magnetic resonance and scanning electron microscopy with X-ray analysis. The evolutions of the output concentrations and of the mineralogy over the injection process could be well predicted with the geochemical modeling software CHESS. Experimental results of the campaign, in conjunction with results from mineralogical and microstructural characterizations, made it possible to reveal what the main parameters are that govern expansion. Thanks to the original protocol we developed, expansion or development of stresses started immediately after the injection of solution, stabilized after a few days to a few dozen days, and crystallization occurred homogeneously throughout the height of the sample. One interesting conclusion is that, even when ettringite crystallizes in macropores, i.e., outside of the C-S-H gel porosity, ettringite can lead to an expansion. Also, we showed that gypsum crystallization contributes to expansion. In isochoric testing, we showed that both crystallization of ettringite and of gypsum can induce stresses, and that the magnitude of those stresses is linearly related to the volume of those crystals formed. The conclusions drawn from this experimental study make it possible to better understand the physical processes through which crystallization induces expansion or stresses in porous solids, and thus to orient the modeling of sulfate attacks in cement-based materials

Une augmentation de la température à jeune âge du béton peut être causée par la chaleur d’hydratation dans le cas d’éléments massifs ou par l’application d’un traitement thermique dans l’industrie de la préfabrication. Lorsque le couple critique température maximale/durée de maintien est dépassé, il y a formation différée de l’ettringite (DEF) expansive pouvant fissurer les pièces. Les travaux présentés dans ce mémoire ont pour but principal d’établir une limite sécuritaire pour des mélanges V-S pour béton de masse et V-P pour béton préfabriqué régulièrement utilisés par le Ministère des Transports du Québec. Ces bétons utilisent des liants binaires composés de fumée de silice de type GUb-SF et des liants ternaires composés de fumée de silice et de cendres volantes ou de laitier de haut-fourneau. La norme canadienne actuelle (CSA A23.1-14 et CSA A23.4-16) impose une limite fixe de température qui ne dépend ni de la durée de traitement ni du type de liant utilisé. Le lien, souvent énoncé dans la littérature, entre la réponse d’un liant à un traitement thermique et sa composition chimique et minéralogique, déterminé respectivement par fluorescence X et diffraction des rayons X couplée par la méthode de calcul Rietveld, a pu être confirmé. Le rapport SO3 solubles/Al2O3 est notamment ce qui permet la meilleure estimation de la sensibilité d’un liant. Le processus de formation différée de l’ettringite est lent et peut prendre plusieurs années. Donc, pour étudier le phénomène, des méthodes d’essais accélérés ont été testées. Des méthodes ont ainsi pu être proposées pour de futurs tests. Une méthode d’essai rapide d’expansion de barres de mortier permet d’identifier les liants les plus sensibles à la DEF. La formation de la DEF dans les liants les moins sensibles peut être appréciée par le gain de masse de prismes de béton et leur observation microstructurale au microscope électronique à balayage (MEB). Une méthode sur bétons de masse et bétons préfabriqués permet de classer le degré de sensibilité d’un liant face à la DEF selon le gain de masse des prismes de béton. Les liants ternaires montrent une bonne résistance face à la DEF. La sensibilité des liants binaires dépend du rapport SO3 solubles/Al2O3 du liant. / Abstract : A heat cure for concrete can be caused by hydration in massive structures or by thermal treatment in prefabrication industry. When the limit couple maximum temperature/duration of treatment is exceeded, the delayed formation of ettringite occurs and leads to cracking in concrete. The main goal of the work presented in this essay is to establish a safe batch limit for some mixtures, VS (mass concrete) and V-P (precast concrete) which are often used by MTQ. These concretes use some cements blended with silica fume and ternary blended cements with silica fume and fly ash or blast furnace slag. Indeed, the current Canadian standard (CSA A23.1) set a limit which doesn’t depend on duration of the treatment nor the type of bender. However, the link between composition of the used bender, with can be determined by X-ray fluorescence and X-ray diffraction, and the response to a thermal treatment has been confirmed. The soluble SO3/Al2O3 ratio allows to estimate if a bender is sensitive to heat cure. The delayed formation of ettringite is a long process which can last a decade. In order to study this phenomenon, several accelerated test methods have been used. Some of them are available for some future tests. An accelerated expansion method using mortar bar allows to spot the DEF-sensitive benders. Delayed ettringite formation in the less sensitive bender can be estimated by weight gain in concrete prisms and by observation with scanning electron microscope (SEM). The sensitivity level of a bender can by estimated using a method based on weight gain. Ternary blended cements show a greater ability to withstand DEF. The sensibility of binary blended cements depends on soluble SO3/Al2O3 ratio.